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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthetic, structural, NMR and catalytic studies of phosphinic amide-phosphoryl chalcogenides (chalcogen = O, S, Se) as mixed-donor bidentate ligands in zinc chemistry
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Synthetic, structural, NMR and catalytic studies of phosphinic amide-phosphoryl chalcogenides (chalcogen = O, S, Se) as mixed-donor bidentate ligands in zinc chemistry

机译：作为锌化学中混合施主双齿配体的次膦酰胺-磷酰基硫属元素化物（硫属元素= O，S，Se）的合成，结构，NMR和催化研究

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ortho Substituted (diphenylphosphoryl)-, (diphenylphosphorothioyl)- and (diphenylphosphoroselenoyl)- phosphinic amides o-C_6H_4(P(X)Ph_2)(P(O)N'Pr_2) (X = O (20a), S (20b), Se (20c)) were synthesized by ortho directed lithiation of N,N-diisopropyl-P,P-diphenylphosphinic amide (Ph_2P(O)N'Pr_2) followed by trapping with Ph_2PCl and subsequent oxidation of the o-(diphenylphosphine)phosphinic amide (19) with H_2O_2, S8 and Se. The reaction of the new mixed-donor bidentate ligands with zinc dichloride afforded the corresponding complexes [ZnCl_2(P(X)Ph_2)o-C_6H_4(P(O)N'Pr_2)] (21a–c). The new compounds were structurally characterized in solution by nuclear magnetic resonance spectroscopy and in the solid-state by X-ray diffraction analysis of the ligand (20b) and the three complexes (21a–c). The X-ray crystal structure of 20b suggests the existence of a P=O→P(S)–C intramolecular nonbonded interaction. The natural bond orbital (NBO) analysis using DFT methods showed that the stabilization effect provided by a n_O→σ~*_(P–C) orbital interaction was negligible. The molecular structure of the complexes consisted of seven-membered chelates formed by O,X-coordination of the ligands to the zinc cation. The metal is four-coordinated by binding to the two chlorine atoms showing a distorted tetrahedral geometry. Applications in catalysis revealed that hemilabile ligands 20a–c act as significant promoters of the addition of diethylzinc to aldehydes, with 20a showing the highest activity. Chelation of Et_2Zn with 20a was evidenced by NMR spectroscopy.
机译：邻位取代的（二苯基磷酰基）-，（二苯基磷硫磺酰基）-和（二苯基磷杂环戊酰基）-次膦酰胺o-C_6H_4（P（X）Ph_2）（P（O）N'Pr_2）（X = O（20a），S（20b）， Se（20c））是通过N，N-二异丙基-P，P-二苯基次膦酰胺（Ph_2P（O）N'Pr_2）的直接定向锂化反应制备的，然后用Ph_2PCl捕获并随后氧​​化邻（二苯基膦）次膦酰胺（19）具有H_2O_2，S8和Se。新的混合给体二齿配体与二氯化锌的反应提供了相应的配合物[ZnCl_2（P（X）Ph_2）o-C_6H_4（P（O）N'Pr_2）]（21a–c）。新化合物在溶液中通过核磁共振波谱进行了结构表征，在固态中通过对配体（20b）和三个配合物（21a–c）的X射线衍射分析进行了表征。 20b的X射线晶体结构表明存在P = O→P（S）–C分子内非键相互作用。使用DFT方法进行的自然键轨道（NBO）分析表明，由n_O→σ〜* _（P–C）轨道相互作用提供的稳定作用可忽略不计。配合物的分子结构由通过配体与锌阳离子的O，X配位形成的七元螯​​合物组成。通过结合到两个氯原子上显示出扭曲的四面体几何形状，金属被四配位。在催化方面的应用表明，半不稳定的配体20a–c是向乙醛中添加二乙基锌的重要促进剂，其中20a的活性最高。 Et_2Zn与20a的螯合通过NMR光谱证明。

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